JPH11170456A - Polyolefin resin laminate oriented film superior in transparency - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin resin laminated film superior in antistatic properties, process stability and transparency, having no problems of whitening by bleed, blocking and the like and adverse effect on bonding properties and printability, and not generating smoke at the time of processing. SOLUTION: An antistatic resin layer, which is composed of 55-90 wt.% polypropylene resin, 5-40 wt.% aromatic ring containing polyether ester amid of 160 deg.C melting point or lower, 3-20 wt.% polyamide resin, a number-average molecular weight of 800-25,000 modified low-molecular polypropylene having an acid value of 5-15, and one kind or more of 1-20 wt.% modified low- molecular polypropylene selected out of modified low molecular polypropylene having a number average molecular weight of 800-28,000 prepared by using alkanolamine and/or a hydroxy group containing polyoxyakylene compound and modifying the above polypropylene, is formed on an outermost layer and an oriented polyolefin resin laminate oriented film of superior transparency is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin laminated stretch film excellent in transparency. More specifically, it has excellent antistatic properties and transparency, has no problems of whitening and blocking due to bleeding, has excellent printability and vapor deposition suitability, has no problems such as smoke or roll stains during processing, and has excellent processing stability. The present invention relates to a polyolefin resin laminated stretched film having excellent transparency which can be suitably used as a packaging material, a tape material and the like.

[0002]

2. Description of the Related Art Stretched films of polyolefins are widely used as packaging materials for foods and fibers because of their good transparency, rigidity and moisture resistance. The polyolefin film generates remarkably static electricity as it is, and thus has various problems such as adhesion of dust, electric shock to a human body during processing, and scattering of ink during printing. For this reason, an anionic, cationic or amphoteric surfactant is kneaded and mixed, and is transferred to the surface to exhibit antistatic properties, or the surfactant is applied to the surface to exhibit antistatic properties. Generally done. However, since such surfactants have a relatively small molecular weight, they volatilize during film production, or migrate to the surface over time after being formed into a film, contaminate the film surface, and cause blocking and whitening. In addition, there is a problem that the adhesiveness, printability, vapor deposition and the like are deteriorated. In addition to the polyolefin-based resin stretched film using the surfactant, as a polyolefin-based resin (stretched) film having excellent antistatic properties, a resin having one or more specific functional groups in a thermoplastic resin may be used. And a film obtained by adding a special modified resin. (JP-A-62-121717, JP-B-1-29820, JP-A-5-1930)
However, these methods have problems such as poor compatibility with the polyolefin resin, poor transparency, and insufficient heat resistance to generate decomposed products during production, making stable production impossible.

[0003]

SUMMARY OF THE INVENTION In view of the above problems, the present invention has excellent antistatic properties and transparency, and has whitening due to bleeding.
No blocking problem, excellent printability, deposition suitability,
It is another object of the present invention to provide a polyolefin-based resin laminated film which is free from problems such as smoke and roll contamination during processing and has excellent processing stability.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polypropylene resin, a specific aromatic ring-containing polyetheresteramide and a polyamide resin, and a specific modified low molecular weight polypropylene It has been found that the above problem can be solved by laminating an antistatic resin layer composed of a mixture of the above on the surface of a polyoff-in film and stretching it in at least one axial direction, and has reached the present invention. That is, the stretched polyolefin-based resin laminate film of the present invention has at least one antistatic resin layer formed of the following components A, B, C and D on the outermost layer, and is formed in at least one direction. And the haze is 20 or less. Component A: 55 to 90% by weight of a polypropylene resin Component B: 5 to 40% by weight of an aromatic ring-containing polyetheresteramide having a melting point of 160 ° C. or less Component C: 3 to 20% by weight of a polyamide resin Component D: The following component (d1) And at least one modified low molecular weight polypropylene selected from (d2) and 1 to 20% by weight Component (d1): a modified low molecular weight polypropylene having a number average molecular weight of 800 to 25,000 and an acid value of 5 to 150. Component (d2): A part or all of the (anhydrous) carboxylic acid unit of the component (d1) is modified with an alkanolamine and / or a hydroxyl group-containing polyoxyalkylene compound, and has a number average molecular weight of 800.
~ 28,000 modified low molecular weight polypropylene.

[0005]

DETAILED DESCRIPTION OF THE INVENTION [I] Polyolefin Laminated Stretched Film (1) Layer Structure (A) Base Layer (a) Material In the polyolefin resin laminate stretched film of the present invention, the polyolefin resin used as a base layer is as follows. , Propylene-based resins such as propylene homopolymer and propylene and other α-olefins (eg, ethylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1- Random copolymer or block copolymer with one or more types such as dodecene,
And polyolefin resins such as high-density polyethylene, medium-low pressure low density polyethylene, and high pressure low density polyethylene. Among these, propylene resins such as propylene homopolymer, propylene / ethylene random copolymer, propylene / 1-butene random copolymer, and propylene / ethylene / 1-butene random copolymer are preferred. These may be used alone or as a mixture of two or more as needed.

(B) Additives Known other resin additives can be optionally added to the polyolefin resin used in the base layer as long as the properties of the present invention are not impaired. As the additive,
Examples include antioxidants, neutralizing agents, lubricants, nucleating agents, fillers such as silica and organic crosslinked fine particles, ultraviolet absorbers, light stabilizers, plasticizers, mold release agents, and flame retardants.

(B) Antistatic Resin Layer In the stretched polyolefin resin laminated film of the present invention, the antistatic resin composition constituting the antistatic resin layer comprises the following components A, B, C and D.

(A) Component A: Polypropylene Resin In the laminated stretched polyolefin resin film of the present invention, the polypropylene resin of Component A constituting the antistatic resin layer may be propylene homopolymerized extension or propylene and another type of propylene. The above-mentioned random copolymer or block copolymer with α-olefin can be exemplified. Examples of the other α-olefin include ethylene, 1-butene, 4-methyl-1-pentene, 1-pentene, and 1-pentene.
Octene, 1-decene, 1-dodecene and the like can be mentioned. Among them, propylene homopolymer, propylene / ethylene random copolymer, propylene / 1
-Butene random copolymer, propylene / ethylene / 1
-Butene random copolymer. Melt flow rate (MF) of polypropylene resin used as component A
R) is usually 0.5 to 150 g / 10 min, preferably 1 to 100 g / 10 min. The melt flow rate is JIS-K6758 (temperature 230
° C and a load of 2.16 kgf). The content of the component A in the antistatic resin layer is usually 55
９０90% by weight, preferably 60-85% by weight. If the amount of the component A is less than the above range, the mechanical strength of the final laminated film is poor, and if it exceeds the above range, the antistatic property is reduced.

(B) Component B: Aromatic ring-containing polyetheresteramide having a melting point of 160 ° C. or less In the polyolefin resin laminated stretched film of the present invention, the melting point of the component B constituting the antistatic resin layer is 160.
The aromatic ring-containing polyetheresteramide having a temperature of not more than ° C is composed of a polyamide (b1) having a carboxyl group at both terminals and an alkylene oxide adduct of a bisphenol (b2).

Polyamide having carboxyl groups at both ends
The polyamide (b1) having a carboxyl group at both ends constituting the aromatic ring-containing polyetheresteramide having a melting point of component (B1) component B having a melting point of 160 ° C. or lower includes (1) a lactam ring-opened polymer, and (2) amino It is a polycondensate of a carboxylic acid or (3) a polycondensate of a dicarboxylic acid and a diamine. Examples of the lactam constituting the lactam ring-opened polymer of the above (1) include caprolactam, enantholactam, uralolactam, undecanolactam and the like. Examples of the aminocarboxylic acid constituting the polycondensate of the aminocarboxylic acid of the above (2) include ω-aminocaproic acid,
ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Examples of the dicarboxylic acid constituting the polycondensate of the dicarboxylic acid and the diamine of the above (3) include adipic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, isophthalic acid, and the like. Examples include methylene diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine, and the like. Two or more of those exemplified as the amide-forming monomers may be used. Preferred among these are caprolactam, 12-aminododecanoic acid,
And adipic acid-hexamethylenediamine, with caprolactam and 12-aminododecanoic acid being particularly preferred.

The polyamide (b1) having a carboxyl group at both ends is prepared by using a dicarboxylic acid component having 4 to 20 carbon atoms as a molecular weight modifier and subjecting the amide-forming monomer to ring opening in the presence of the diamide. It can be obtained by polymerization or polycondensation. Examples of the dicarboxylic acids having 4 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, terephthalic acid, and isophthalic acid. , Phthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, and 1,
4-cyclohexanedicarboxylic acid, dicyclohexyl-
Alicyclic dicarboxylic acids such as 4,4-dicarboxylic acid and 3-
And alkali metal salts of 3-sulfoisophthalic acid such as sodium sulfoisophthalate and potassium 3-sulfoisophthalate. Of these, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and particularly preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and
-Sodium sulfoisophthalate. The number average molecular weight of the polyamide (b1) having a carboxyl group at both ends is 200 to 5,000, preferably 500 to 3,
000. If the number average molecular weight of the above (b1) is less than the above range, the heat resistance of the polyetheresteramide itself will decrease, and if it exceeds the above range, the reactivity will decrease. I need.

[0012] Bisphenols with alkylene oxide
The bisphenols of the alkylene oxide adduct (b2) of bisphenols, which is the other component constituting the additive (b2) component B, include bisphenol A (4,4'-dihydroxydiphenyl-2,2-propane), Bisphenol F (4,4'-dihydroxydiphenylmethane), bisphenol S (4,4'-dihydroxydiphenylsulfone), 4,4'-dihydroxydiphenyl-2,2-
Butane and the like are mentioned, and among them, particularly preferred is bisphenol A. Examples of the alkylene oxide (b2) include ethylene oxide, propylene oxide, 1,2- or 1,4-butylene oxide, and a mixture of two or more thereof. Preferred among these is ethylene oxide. The number average molecular weight of the above (b2) is usually from 300 to 5,000, preferably from 1,000 to 3,000. When the number average molecular weight is less than the above range, the antistatic property becomes insufficient, and when the number average molecular weight exceeds the above range, the reactivity decreases, so that it takes a lot of time to produce polyetheresteramide.

The amount of the alkylene oxide adduct of bisphenols (b2) in the aromatic ring-containing polyetheresteramide having a melting point of 160 ° C. or less of the specific component B is determined by the polyamide (b1) having a carboxyl group at both ends. It is usually in the range of 20 to 80% by weight, preferably 25 to 75% by weight, based on the total weight of the alkylene oxide adduct of bisphenols and bisphenols (b2). If the amount of (b2) is less than the above range, the antistatic property of the component B is inferior, and if it exceeds the above range, the heat resistance of the component B itself is undesirably reduced.

[0014] The preparation method of the production method component B component B, is not particularly limited, for example, can be exemplified the following method or process. Production method A method in which (b1) is formed by reacting an amide-forming monomer and a dicarboxylic acid, and (b2) is added thereto, and a polymerization reaction is performed at high temperature and under reduced pressure. Production Method The amide-forming monomer and dicarbonic acid and (b2) are simultaneously charged into a reaction vessel, and pressure reaction is performed at a high temperature in the presence or absence of water to produce (b1) as an intermediate, and then the pressure is reduced. A method of performing a polymerization reaction of (b1) and (b2) below.

In the above-mentioned polymerization reaction, a known esterification catalyst is usually used. Examples of the catalyst include an antimony catalyst such as antimony trioxide, a tin catalyst such as monobutyltin oxide, a titanium catalyst such as tetrabutyl titanate, a zirconium catalyst such as tetrabutylzirconate, and a metal acetate such as zinc acetate. And the like. The amount of these used is usually 0.1 to 5% by weight based on the total weight of (b1) and (b2). The reduced viscosity of the component B (0.5% by weight m-cresol solution, 25 ° C.) is not particularly limited, but is usually 0.5 to 4.0, preferably 0.5 to 4.0.
6 to 3.0. If the reduced viscosity is less than 0.5, heat resistance is poor, and if it exceeds 4.0, moldability tends to be reduced.
The content of the aromatic ring-containing polyetheresteramide having a melting point of component B of 160 ° C. or lower in the antistatic resin layer is usually 5 to 40% by weight, preferably 5 to 30% by weight. 5
If the amount is less than 40% by weight, the antistatic property is insufficient.
Exceeding the above range lowers the mechanical strength of the final laminated film.

The aromatic ring-containing polyetheresteramide
Melting point In the present invention, the melting point of the aromatic ring-containing polyetheresteramide of Component B is 160 ° C. or lower, preferably 140 ° C. or lower.
It is essential that the temperature is 155 ° C. When the melting point exceeds 160 ° C., the antistatic property of the final laminated film becomes insufficient.
The melting point is measured by a differential calorimeter (DSC).
It is a value obtained from the peak top value of the endothermic peak on the high temperature side.

(C) Component C: Polyamide Resin In the laminated stretched polyolefin resin film of the present invention, the polyamide resin of Component C constituting the antistatic resin layer includes (1) a lactam ring-opening polymer, (2) )
Examples include a polycondensate of an aminocarboxylic acid or (3) a polycondensate of a dicarboxylic acid and a diamine. Specific examples include nylon 66, nylon 69, and nylon 6.1.
0, nylon 6,12, nylon 6, nylon 11, nylon 12, nylon 46 and the like. In addition, nylon 6/66, nylon 6/10, nylon 6/12,
Copolyamides such as nylon 6/66/12 can also be used. Further, there may be mentioned aromatic-containing polyamides obtained from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and meta-xylene diamine or aliphatic diamine. Of these, nylon 66, nylon 6 and nylon 12 are particularly preferred.

Relative viscosity The relative viscosity of component C (98% sulfuric acid, concentration 1 g / 100 m
1, 25 ° C.) is usually 5 or less, preferably 1.2 to 4. If the relative viscosity exceeds the above range, the moldability may decrease. The content of the polyamide resin of Component C in the antistatic resin layer in the polyolefin-based laminated stretched film of the present invention is usually 3 to 20% by weight, preferably 3 to 1% by weight.
5% by weight. If the content of the polyamide resin of the component C is less than the above range, the antistatic property becomes insufficient, and if it exceeds the above range, the mechanical strength of the final stretched resin laminate film is reduced.

(D) Component D: Modified Low Molecular Weight Polypropylene In the stretched polyolefin resin laminated film of the present invention, the modified low molecular weight polypropylene of Component D constituting the antistatic resin layer includes the following components (d1) and At least one selected from (d2) is used. Component (d1): Modified low molecular weight polypropylene having a number average molecular weight of 800 to 25,000 and an acid value of 5 to 150. Component (d2): Modified low molecular weight having a number average molecular weight of 800 to 28,000 in which part or all of the (anhydride) carboxylic acid unit of component (d1) is modified with an alkanolamine and / or a hydroxyl group-containing polyoxyalkylene compound. polypropylene.

Component (d1) The component (d1) has a number average molecular weight of 700 to 2 obtained by a polymerization method or a thermal degradation method of high molecular weight polypropylene.
A low-molecular-weight polypropylene of 000 is grafted with an α, β-unsaturated carboxylic acid and / or an anhydride thereof, if necessary, in the presence of an organic peroxide by a solution method or a melt method. It can be obtained by denaturation. From the viewpoint of easy modification, it is preferable to use a low-molecular-weight polypropylene obtained by a thermal degradation method. The low molecular weight polypropylene obtained by the thermal degradation method can be obtained, for example, according to the method described in JP-A-3-62804. The α, β-unsaturated carboxylic acid and / or its anhydride used for the modification include (meth)
Acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous)
Examples include itaconic acid and citraconic anhydride. Among these, maleic acid (anhydride) is preferred. These α, β-unsaturated carboxylic acids and / or
Alternatively, the amount of the anhydride is usually 1 to 25% by weight, preferably 3 to 20% by weight based on the weight of the low molecular weight polypropylene.

Component (d1) obtained by the above method
Has a number average molecular weight of usually 800 to 25,000, preferably 1,000 to 20,000. When the number average molecular weight is less than the above range, heat resistance is poor, and when the number average molecular weight exceeds the above range, the effect as a compatibilizer becomes poor, and the mechanical properties of the final stretched laminated resin film are reduced, or the stretched final laminated resin film is reduced. Problems such as roll contamination occur during the production of. The measurement of the number average molecular weight is performed by gel permeation chromatography (GPC). The acid value of the component (d1) is 5 to 150, preferably 10 to 1
00 is within the range. If the acid value is less than the above range, the effect as a compatibilizer is poor, and if the acid value exceeds the above range, the hue is deteriorated, and there is a problem that the final stretched resin laminate film is colored. The acid value is a value measured by dissolving the component (d1) in hot xylene and titrating with a 0.1N methanolic KOH solution using phenolphthalein as an indicator.

Component (d2) The component (d2) is obtained by subjecting a part or all of the (anhydride) carboxylic acid unit of the component (d1) to secondary modification with an alkanolamine and / or a hydroxyl group-containing polyoxyalkylene compound. Can be obtained by: Examples of the alkanolamine include monoethanolamine, monoisopropanolamine, diethanolamine, diisopropanolamine, and the like. Of these, particularly preferred is monoethanolamine. Examples of the polyoxyalkylene compound include compounds having hydroxyl groups at both ends, such as polyethylene glycol and polypropylene glycol, and compounds in which the above hydroxyl groups are replaced with amino groups or epoxy groups. Further, compounds having active hydrogen such as alcohols (methanol, ethanol, butanol, octanol, lauryl alcohol, 2-ethylhexyl alcohol, etc.) and phenols (phenol, alkylphenol, naphthol, phenylphenol, benzylphenol, etc.) have alkylene oxides. In addition, a polyalkylene compound having a hydroxyl group at one terminal is basically mentioned.

The molecular weight of these polyoxyalkylene compounds is usually from 300 to 5,000. The secondary modification rate is not particularly limited, but it is preferable that 10 to 100 mol% of the (anhydrous) carboxylic acid unit of the component (d1) is imidized or esterified. The number average molecular weight of component (d2) is usually from 800 to 28,000, preferably from 1,200 to 25,000. When the number average molecular weight is less than the above range, the ripening resistance decreases, and when the number average molecular weight exceeds the above range, the effect as a compatibilizer becomes poor. The components (d1) and (d2) of the modified low molecular weight polypropylene exemplified above may be used in combination of two or more. In addition, you may use the modified low molecular weight polypropylene which has a carboxyl group, a hydroxyl group, and all polyoxyalkylene groups in a molecule | numerator.

Content of Component D The content of Component D in the antistatic resin composition constituting the antistatic resin layer in the present invention is usually 1 to 20% by weight, preferably 3 to 15% by weight. . When the content of the component D is less than the above range, the compatibilizing effect becomes small, and phase separation of the antistatic resin composition easily occurs. If it exceeds the above range, the mechanical strength of the final laminated film will decrease.

(E) Component E: a metal salt composed of a halide of an alkali metal and / or an alkaline earth metal The antistatic resin composition constituting the antistatic resin layer in the present invention contains an antistatic resin. In order to further improve the properties, a metal salt composed of a halide of an alkali metal and / or an alkaline earth metal may be contained as the component E. Examples of the component E include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, and magnesium bromide. Preferred among these are lithium chloride, sodium chloride and potassium chloride. The content of the component E is usually 0.01 to 3% by weight, preferably 0.05 to 2% by weight, based on the total weight of the components A, B, C and D. If the content of the component E is less than the above range, no effect will be exhibited, and if it exceeds the above range, it will precipitate on the film surface, causing surface contamination and whitening. The method for adding the component E is not particularly limited. However, it is preferable that the component E is previously dispersed in the polyetheresteramide of the component B from the viewpoint of easy dispersion in the composition. When the component E is dispersed in the component B, a method in which the component E is previously added and dispersed during the polymerization of the component B is particularly preferable.

(F) Component F: Surfactant In the stretched polyolefin resin laminated film of the present invention, a nonionic, anionic, A cationic or amphoteric surfactant may be contained to further improve the antistatic property. As nonionic surfactants, higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polyethylene glycol type nonionic surfactants such as polypropylene glycol ethylene oxide adducts, polyethylene oxide, Examples thereof include fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbit and sorbitan, alkyl ethers of polyhydric alcohols, and polyhydric alcohol-type nonionic surfactants such as aliphatic amides of alkanolamines.

Examples of the anionic surfactant include carboxylate salts such as alkali metal salts of higher fatty acids, sulfate salts such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates, and alkyl sulfonates. And sulfonate salts such as paraffin sulfonate salt, and phosphate ester salts such as higher alcohol phosphate ester salt. Examples of the cationic surfactant include quaternary ammonium salts such as an alkyltrimethylammonium salt.

Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyl dimeter betaines and higher alkyl dihydroxyethyl betaines. These may be used alone or in combination of two or more. Of these, preferred are anionic surfactants, and particularly preferred are sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates.

The content of the above-mentioned component F is as follows: component A, component B,
Usually 0.1 to 5 based on the total weight of component C and component D
%, Preferably 0.4 to 3% by weight. If the content of the component F is less than the above range, the effect of improving the antistatic property cannot be expected. On the other hand, if it exceeds the above range, it is deposited on the film surface to cause problems of surface contamination and self-generation, and the mechanical strength of the final laminated film is inferior. The method of adding the component F is not particularly limited, but it is preferable that the component F is previously dispersed in the component A or the component B in order to perform effective dispersion in the composition.

(G) Antistatic resin composition In the polyolefin resin laminated stretched film of the present invention, the antistatic resin composition constituting the antistatic resin layer is prepared by using the various components described above by using various known mixers. Can be produced by kneading. Examples of the mixer include a single-screw extruder, a twin-screw extruder, a Brabender, a kneader, and a Banbury mixer. The order of adding the various components at the time of kneading is not particularly limited. For example, a method of blending and kneading components A to D at once, blending and kneading a small amount of component A and components B to D, A method in which the remaining component A is kneaded, a method in which the components B to D are preliminarily blended, kneaded, and then the component A is kneaded. The above methods are methods called master batch or master pellet. Among these, the method is particularly preferable because it has good dispersibility, and is excellent in permanent antistatic properties and mechanical strength of the final stretched resin laminated film. As a method for obtaining the antistatic resin composition used in the stretched polyolefin-based resin film of the present invention via a master batch, for example, 0 to 50 parts by weight of Component A, preferably 5 to 20 parts by weight, 5 to 40 parts by weight of B, 3 to 20 parts by weight of component C and 1 to 20 parts by weight of component D are blended and kneaded to form a master batch.
It can be manufactured by blending and kneading the master batch with the component A. Such a method is particularly advantageous in that a small amount of the component B to the component D can be uniformly dispersed in a large amount of the component A, and the antistatic resin composition used for the stretched polyolefin-based stretched film of the present invention. Particularly preferred as a production method.

(H) Other additives In addition, the antistatic resin composition used in the stretched polyolefin resin laminated film of the present invention, depending on various uses, is within a range that does not impair the properties of the composition. Other known resin additives can be optionally added. Examples of the additives include antioxidants, neutralizing agents, lubricants, nucleating agents, fillers such as silica and organic crosslinked fine particles, ultraviolet absorbers, light stabilizers,
Plasticizers, release agents, flame retardants and the like can be mentioned.

(H) Other additives In addition, the antistatic resin composition used in the stretched polyolefin-based resin film of the present invention, depending on various uses, is provided within a range that does not impair the properties of the composition. Other known resin additives can be optionally added. Examples of the additives include antioxidants, neutralizing agents, lubricants, nucleating agents, fillers such as silica and organic crosslinked fine particles, ultraviolet absorbers, light stabilizers,
Plasticizers, release agents, flame retardants and the like can be mentioned.

(2) Film formation (A) Molding A method for producing a polyolefin-based laminated stretched film of the present invention, except that an antistatic resin composition comprising the components A, B, C and D is used. Is not particularly limited, and various known film forming methods can be used. That is, after preparing a non-stretched sheet or film in advance, a method of stretching in a separate process, and a stretching process is included in the film production process, for example, a method such as an inflation method, a tubular method, and a tenter method. Can be mentioned. In any of these methods, a laminated film can be formed by extruding a resin while laminating the resin from a die capable of co-extrusion.

(B) Stretching The stretched polyolefin-based stretched film of the present invention must be stretched in at least one direction. In the case of the biaxially stretched film by the tenter method, only the base layer is extruded, and after stretching this in the flow direction between heating rolls, laminating an antistatic resin layer, and stretching in the transverse direction with a tenter type oven. It is also possible to produce the desired laminated stretched film. The stretching ratio is 2 to 20 times, preferably 3 to 15 times in the case of uniaxial stretching, and 2 to 15 times, preferably 3 to 1 in each direction in the case of biaxial stretching.
It is 0 times. The polyolefin-based laminated stretch film having excellent antistatic properties of the present invention can be obtained for the first time through such a stretching step. That is, when the stretching ratio is less than 2, the antistatic performance becomes insufficient. Moreover, the polyolefin-based resin laminated stretched film of the present invention may be subjected to a surface treatment such as a corona treatment or a flame treatment, depending on the use and purpose. In this case, it may be the surface on the antistatic resin layer side or the back surface where the antistatic resin layer is not laminated (including lamination on one side).

(C) Thickness The thickness of the base layer is not limited, but is usually 8 to 100.
μm, preferably 10 to 80 μm. Further, there is no limitation on the thickness of the final polyolefin resin laminated film in which the antistatic resin layer is laminated on the base layer, but the thickness of the final polyolefin resin laminated film is usually 8
The thickness of the antistatic resin layer on the surface (the total thickness in the case of both surface layers) is 0.5 to 50% with respect to the thickness of the final polyolefin resin laminated film. Is preferable, and especially 2 to
30% is preferable from the viewpoint of antistatic property and mechanical strength.

[II] Applications The laminated stretched polyolefin resin film of the present invention has excellent antistatic properties and transparency, has no problems of whitening and blocking due to bleeding, has excellent printability and suitability for vapor deposition, and further emits smoke during processing. Since it is free from problems such as ink and roll contamination and has excellent processing stability, it can be suitably used as a packaging material, a tape material and the like.

[0037]

EXAMPLES The laminated stretched polyolefin resin film of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. In the examples, "parts" indicates parts by weight, and "%" indicates% by weight.

[I] Evaluation Method The determination of the moldability and the various physical properties of the obtained film were tested according to the following test methods and evaluated according to the following criteria. (1) Smoke emission during molding The amount of smoke emitted near the die exit was visually determined. ：: Smoke is hardly observed △: Smoke is slightly observed ×: Smoke is observed (2) Roll dirt The degree of dirt on the casting roll where the sheet (or film) extruded from the die exit comes into contact first is visually observed. Judged by. ：: Almost no dirt observed △: Slight dirt was observed, but no level of continuous production failure ×: Dirt was observed, level that could not be continuously produced

(3) Haze The haze of one film was measured according to JIS-K6714. (4) Whitening After measuring the haze of one film, the film was stored in an oven at 40 ° C. for one week, and the haze was measured in the same manner. The difference in haze was defined as whitening. (5) Blocking property Two films were stacked so that the contact area was 10 cm ^2, and this was sandwiched between two glass plates, and 50 g / cm
^After applying a load of ² and leaving it to stand in an atmosphere of 40 ° C. for 7 days, the maximum load when peeling off was measured with a shopper type tester. (6) Antistatic properties In a constant temperature / humidity room at 23 ° C and 50% RH, Shishido Shokai Co., Ltd.
Static Honest Meter (TYPE-5-10)
In 9), half-lives were measured immediately after molding and after aging at 40 ° C. for 1 day. (7) Wetting tension The film prepared so that the wetting tension was 41 dyn / cm was aged at 40 ° C. for 7 days, and the wetting tension was measured.

[II] Raw Materials [Production of Polyetheresteramide (B)] Production Example 1 A stainless steel autoclave having a content of 3 liters was placed in a stainless steel autoclave.
-113 parts of caprolactam, 32 parts of adipic acid, 330 parts of bisphenol A ethylene oxide adduct having a number average molecular weight of 1,500, 0.3 parts of "Irganox 1010" (antioxidant, manufactured by Ciba Geigy), 0.5 part of zirconyl acetate And 6 parts of water, and after purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 2 hours under pressure and closed to form a homogeneous solution. afterwards,
Polymerization was performed at 245 ° C. under a reduced pressure of 1 mmHg or less for 3.5 hours to obtain a polyetheresteramide of the present invention.
Its melting point is 155 ° C (measured by DSC, the same applies hereinafter)
And the reduced viscosity is 1.80 (η _{SP /} C, C = 0.5%, m
Cresol solution, 25 ° C., the same applies hereinafter). This polyetheresteramide is abbreviated as [B-1] below.

Production Example 2 In a stainless steel autoclave having a content of 3 liters, 1
110 parts of 2-aminododecanoic acid, 16.3 of adipic acid
And 0.3 part of "Irganox 1010" were charged, and the mixture was purged with nitrogen, and heated and stirred at 220 ° C. for 5 hours while sealing under pressure to obtain 117 parts of a polyamide oligomer having a carboxyl group at both terminals and having an acid value of 110. Next, the number average molecular weight is 1,50.
Bisphenol A ethylene oxide adduct 165
Part, zirconyl acetate 0.5 part, 245 ° C, 1 mm
Polymerization was performed for 5 hours under reduced pressure of not more than Hg to obtain a polyetheresteramide of the present invention. Its melting point is 15
At 0 ° C., the reduced viscosity was 1.70. This polyetheresteramide is abbreviated as [B-2] below.

Production Example 3 In a stainless steel autoclave having a content of 3 liters,
-105 parts of caprolactam, 24.6 parts of adipic acid,
0.3 parts of “Irganox 1010” and 6 parts of water were charged, and after purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours while sealing under pressure to obtain 126 parts of a polyamide oligomer having a carboxyl group at both ends and having an acid value of 150. Was. Next, 250 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 1,500 and 0.7 parts of zirconyl acetate were added, and 245 was added.
Polymerization was performed for 5 hours at 1 ° C. under a reduced pressure of 1 mmHg or less to obtain a comparative polyetheresteramide. This had a melting point of 175 ° C. and a reduced viscosity of 1.80. This polyetheresteramide is abbreviated as [B-3] below.

Production of Modified Low Molecular Weight Polypropylene (D) Production Example 4 95 parts of a low molecular weight polypropylene having a number average molecular weight of 12,000 and a density of 0.89, obtained by thermal degradation, and 5 parts of maleic anhydride were mixed with nitrogen. The mixture was melted at 180 ° C. in a stream of air, and then a 50% xylene solution in which 1.5 parts of dicumyl peroxide was dissolved was added dropwise over 15 minutes. After the reaction was carried out for 1 hour, the solvent was distilled off. An acid-modified low molecular weight polypropylene was obtained. This had an acid value of 25.7 and a number average molecular weight of 15,000. This modified product is abbreviated as [D-1] below.

Production Example 5 The acid-modified low molecular weight polypropylene 95 obtained in Production Example 4
Part was melted in 100 parts of xylene at 120 ° C. under a nitrogen stream,
Next, 5 parts of monoethanolamine was added dropwise over 15 minutes, and after the reaction was carried out for 1 hour, the solvent and unreacted monoethanolamine were distilled off to obtain a modified low molecular weight polypropylene having a hydroxyl group. This had a hydroxyl value of 25.2 and a number average molecular weight of 16,000. This modified product is abbreviated as [D-2] below.

Production Example 6 The acid-modified low molecular weight polypropylene 95 obtained in Production Example 4
Parts and 50 parts of a 24 mol ethylene oxide adduct of lauryl alcohol are melted at 180 ° C. under nitrogen,
The esterification reaction was carried out under a reduced pressure of mmHg for 5 hours to obtain a polyoxyalkylene-modified low-molecular-weight polypropylene. This had a hydroxyl value of 0.5 and a number average molecular weight of 18,000. From the analysis by NMR,
It was confirmed that the esterification reaction could be performed quantitatively. This modified product is abbreviated as [D-3] below.

[III] Examples and Comparative Examples Example 1 Production of antistatic resin composition Compounded according to the composition shown in Table 1 and kneaded with a twin-screw extruder equipped with a vent set at a temperature of 230 ° C. A pellet-shaped antistatic resin composition was prepared by extruding from a die into a strand and cutting.

The polyolefin resin laminated stretched film
2.4 g / 10 MFR containing an antistatic resin composition having the composition shown in Table 1 as a production surface layer and 0.1% by weight of an antioxidant and 0.05% by weight of calcium stearate as a base layer.
Of propylene homopolymer by melt extrusion at a set temperature of 260 ° C. from an extruder equipped with a T-type die capable of co-extrusion.
A sheet was obtained by quenching with a cooling roll at ℃. This sheet is stretched 5 times in the machine direction using the difference in peripheral speed between the rolls heated to 135 ° C., and subsequently stretched 9 times in the transverse direction at a stretching temperature of 162 ° C. using a tenter type stretching machine. Thus, a biaxially stretched laminated film having a total thickness of 25 μm and having a 2 μm antistatic resin layer on the surface was produced. Next, the surface on the antistatic resin side was subjected to corona discharge treatment so that the wetting tension was 41 dyn / cm. The obtained polyolefin resin laminated stretched film was evaluated, and the results are shown in Table-2.

Example 2 A film was prepared in the same manner as in Example 1 except that the antistatic resin composition of Example 1 was changed to the composition shown in Table 1. The obtained polyolefin resin laminated stretched film was evaluated, and the results are shown in Table-2.

Example 3 A film was prepared in the same manner as in Example 1 except that the antistatic resin composition of Example 1 was changed to the composition shown in Table 1. The obtained polyolefin resin laminated stretched film was evaluated, and the results are shown in Table-2.

Example 4 A film was prepared in the same manner as in Example 1 except that the thickness of the antistatic resin layer serving as the surface layer was changed to 0.5 μm. The obtained polyolefin resin laminated stretched film was evaluated, and the results are shown in Table-2.

Comparative Example 1 A film was prepared in the same manner as in Example 1, except that the composition for preventing turtle turtle in Example 1 was changed to the composition shown in Table 1. (Those whose composition deviates from the claims) The obtained polyolefin-based resin laminated stretched film was evaluated,
Table 2 shows the results.

Comparative Example 2 A film was prepared in the same manner as in Example 1, except that the antistatic resin composition of Example 1 was changed to the composition shown in Table 1. (Those having compositions falling outside the claims and having roll contamination) The obtained polyolefin resin laminated stretched film was evaluated, and the results are shown in Table-2.

Comparative Example 3 A film was prepared in the same manner as in Example 1 except that the antistatic resin composition of Example 1 was changed to the composition shown in Table 1. (The melting point of component (B) exceeds 160 ° C)
The obtained polyolefin resin laminated stretched film was evaluated, and the results are shown in Table-2.

Comparative Example 4 An antistatic resin composition having the composition shown in Table 1 to be a surface layer and a polypropylene (F by Nippon Polychem Co., Ltd.) to be a base layer
L6CK) was melt-extruded at a set temperature of 260 ° C. from an extruder equipped with a T-die capable of co-extrusion, and quenched by a cooling roll at 20 ° C. to obtain a film that was not directly stretched. This film was a non-stretched film having a total thickness of 25 μm and having a 2 μm antistatic resin layer on the same surface as in Example 1. The obtained polyolefin resin laminated stretched film was evaluated, and the results are shown in Table-2.

Comparative Example 5 0.1% by weight of antioxidant, 0.1% of calcium stearate.
M containing 0.5% by weight of a glycerin monofatty acid ester type antistatic agent and 0.5% by weight of a stearyldiethanolamine fatty acid ester type antistatic agent.
Propylene homopolymer [A-2.4 g / 10 min.
3] was melt-extruded at a set temperature of 260 ° C. from an extruder equipped with a T-shaped die, and rapidly cooled with a cooling roll at 20 ° C. to form a sheet. This sheet is stretched 5 times in the flow direction by utilizing the peripheral speed difference between the rolls heated to 135 ° C.
Subsequently, the film was stretched 9 times in the transverse direction at a stretching temperature of 162 ° C. with a tenter-type stretching machine to produce a biaxially stretched single-layer film having a total thickness of 25 μm. Next, a corona discharge treatment was performed on one surface so that the wetting tension was 41 dyn / cm. The obtained polyolefin resin laminated stretched film was evaluated, and the results are shown in Table-2.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

The polyolefin resin laminated stretched film of the present invention is excellent in antistatic properties, has no problem of whitening due to bleeding, blocking, adhesion and printability, and further has problems such as smoke during processing. It is excellent in processing stability and can be suitably used as a packaging material, a tape material and the like.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 77:00 23:26) B29K 23:00 77:00 B29L 9:00 (72) Inventor Eiichi Chida Hitotsubashino, Higashiyama-ku, Kyoto-shi, Kyoto 11 Sanyo Chemical Industry Co., Ltd. at 11 Honcho

Claims (2)

[Claims] An outermost layer is formed with at least one antistatic resin layer comprising the following components A, B, C and D, stretched in at least one direction, and has a haze of 20 or less. Characterized as a multi-layer stretched polyolefin resin film with excellent transparency. Component A: 55 to 90% by weight of a polypropylene resin Component B: 5 to 40% by weight of an aromatic ring-containing polyetheresteramide having a melting point of 160 ° C. or less Component C: 3 to 20% by weight of a polyamide resin Component D: The following component (d1) And at least one modified low molecular weight polypropylene selected from (d2) and 1 to 20% by weight Component (d1): a modified low molecular weight polypropylene having a number average molecular weight of 800 to 25,000 and an acid value of 5 to 150.
Component (d2): Modified low molecular weight having a number average molecular weight of 800 to 28,000 in which part or all of the (anhydride) carboxylic acid unit of component (d1) is modified with an alkanolamine and / or a hydroxyl group-containing polyoxyalkylene compound. polypropylene. 2. The stretched stretched polyolefin resin film having excellent transparency according to claim 1, wherein the thickness of each antistatic resin layer is 0.2 to 15 μm.